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Micellization through complexation of oppositely charged diblock copolymers: Effects of composition, polymer architecture, salt of different valency, and thermoresponsive block
Author(s) -
Gioldasis Christos,
Gergidis Leonidas N.,
Vlahos Costas
Publication year - 2021
Publication title -
journal of polymer science
Language(s) - English
Resource type - Journals
eISSN - 2642-4169
pISSN - 2642-4150
DOI - 10.1002/pol.20200754
Subject(s) - copolymer , micelle , polyelectrolyte , salt (chemistry) , polymer , materials science , chemical engineering , polymer chemistry , divalent , valency , ion , chemical physics , chemistry , organic chemistry , aqueous solution , composite material , linguistics , philosophy , engineering , metallurgy
Abstract The structural and electrical characteristics of polyelectrolyte complex micelles (PCMs) formed by mixing of oppositely charged double hydrophilic copolymers are studied by means of molecular dynamics simulations. In mixtures of linear diblock copolymers we found that the preferential aggregation number N p of PCMs is a universal function of the ratio γ ± of the total positive to total negative charges of the mixture. The addition of divalent salts ions induces a secondary micellization. In mixtures of copolymers bearing a common neutral thermoresponsive block, micelles with contracted corona consisting of thermoresponsive blocks and complex polyelectrolyte core are formed at low salt concentration and temperature far away the biphasic regime. At high salt concentration and temperature in the biphasic regime, reversed micelles are obtained. In equimolar mixtures of linear copolymers with miktoarm stars we found that N p of PCMs decreases as the number of charged branches of miktoarm copolymer increases. The shape of micelles progressively changes from spherical to worm‐like with the increase of number of branches of miktoarm copolymers. Our findings are in full agreement with existing experimental and theoretical predictions and provides new and additional insights.